Water-insoluble azo-dyestuff and fiber dyed therewith



Patented July 23, 1935 WATER-'INSOLUBLE AZO-DYESVTUFF AND YWFIBER DYED; THEREWITH Arthur; Zitscher; Ofienbaoh-on-the-Main', Ger-1, many, assignorjo General Aniline Works, Inc., New York,'N. Yb, a, corporation of Delaware No Drawing. Application June 22, 1933, Serial v No. 677,169. In Germany June 25, 1932 10 Claims. (01. 260.;79

The present invention relates to water-insoluble azo-dyestuffs andqto fiber dyed therewith, more particularly it relates to compounds of the following general formula:

wherein X stands for hydrogen or halogen and R means a radical of the benzene, naphthalene, anth-raquinone or carbazole series.

I have found that valuable water-insoluble azodyestuffs are obtainable bycombining diazo compounds with 4,8-dihydroxy-1,2,5,6-dibenzo-phenazines of the following formula:

strata adapted for the production of lakes, only such components being used which do not.con-' tain any group lending solubility, such as the sulfonic acid or carboxylic acid group.

Inthis manner there are obtained deep redbrown to black dyeings according to the kind of l the diazo compounds frommono-amines, amino- I azo-comp'oundsor poly-amines.

The newv dyestuifs may be used for the preparav tion of fast dyeings and printings on the fiber] or for the preparation ofpigments.

The 4 ,8-dihydroxy- 1 ,2 ,5,6-dibenzo -phena zines are obtainable by converting a 2-amino 3 -hydroXy-naphthalene, the hydrogen atom of the hydroxy group of, which being replaced 'by a suitable radical as; for instance, by acyl or alkyl radicals, into the phenazine according to known methods and then splitting off the radicals linked to the hy'droxy groups. They have, in contrafor the fiber which allows to produce the dyestuffs on the fiber without an intermediate -drying of the grounded goods. The dyeings, thus obtained, possess a better fastness to soaping than those prepared by means of comparable combinations from beta-naphthol.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight, unlessotherwise stated:

(1) 12.75 parts of 1-amino-3-chlorobenzene are diazotized in the usual manner and the diazo solution is coupled with a solutionof 32.5 parts of 4,8-dihydroxy-1,2,5,6-dibenzophenazine in dilute caustic soda solution to which there have been added the quantity of sodium acetate necessary for binding the excess of mineral acid and 5 parts of Turkey red oil. The dyestuff of the following probable formula:

which has been precipitated, is filtered by suctionand washed Well. For the preparation of pigments it is advantageously used in the form of a paste and, when mixed with substrata, it yields a dark brown lake. 7

(2) Well boiled and 'dried cotton yarn is'impregnated with a solution which contains per liter 5 grams of 4,8-dihydroxy-1,2,5,6-dibenzo phenazine, V I I 10 cc. of caustic soda solution of 34 B.,,

10 cc. of Turkey red oil and v 50 grams of sodium chloride, thereupon, the yarn is squeezed'well and developed in a diazo-solution which contains per liter the diazo compound from 1.68 gmmsbf 1-amino-2-methoxye4 -nitrobenzeneand has been neutralized by means of'sodium acetate; the yarn is then rinsed and soap'ed;

There is obtained a deep black-brown dyeing;

' 5 grams of 4,S dihydrQXy-l,2,5,6-dibenzo-phenv azirie, v distinction to beta-naphthoL'a certain affinity 15 cc. of caustic soda solution of 34 B;, 10 cchof Turkey red oil and 20 grams of sodium chloride,

thereupon, it is well freed from water and developed in a diazo-solution which contains per liter the diazo-compound from 3 grams of l-amino-4-benzoylamino-2,5-diethoxy-benzene and has been neutralized by means of sodium acetate; the silk is rinsed, first with cold water and then with hot water, and soaped at 60 C. for a short time.

There is obtained a dark green dyeing.

(4) Spun silk is grounded at 20 C. to 25 C. for 15 to 20 minutes in the proportion of the goods to the liquor 1:30 with a solution which contains per liter 5 grams of 4,8-dihydroxy-1,2,5,6-dibenzo-phenazine,

15 cc. of caustic soda solution of 34 B. and

10 cc. of Turkey red oil, thereupon, 25 grams of sodium chloride per liter are added and the whole is again handled for 15 to 20 minutes. After squeezing, the dyestuff is developed in the course of 30 minutes in a diazosolution which contains per liter the diazo-compound from 1.6 grams of 1-amino-2methoxy4-chlorobenzene and has been neutralized by means of sodium acetate and to which 20 grams of sodium chloride per liter have been added. The dyeing is then rinsed in cold water and acidified with a solution of 3 cc. of concentrated hydrochloric acid per liter, while lukewarm, then it is rinsed again, treated with hot sodium carbonate solution (3 grams of calcined sodium carbonate per liter), rinsed and soaped twice at 7 5 C. to 80 C. and

dried.

There is obtained a dark olive dyeing.

with a solution of 4,8-

the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestufis to alkalies. Substituents of this kind are, forinstance, the sulfonic acid and the carboxylic acid group.

I claim:

1. The water-insoluble azo-dyestufis of the general formula:

wherein X stands for hydrogen or halogen and R means a radical of the benzene, naphthalene, anthraquinone or oarbazole series, yielding, when produced on the fiber, deep red-brown to black dyeings of good fastness properties.

2. The water-insoluble auto-dyestuffs of the general formula:

When wool is grounded X dihydroxy-l,2,5,6-dibenzo-phenazine in caustic soda solution and developed in a diazo-solution which contains the diazo-compound from 1- amino-2-methyl-4-chlorobenzene, a brown dyeing is obtained.

The following table comprises a number of other combinations obtainable according to the present invention:

Diazo compound oi- Combined withsh 1-amino-2,4-dimethyl-benzene 4,8-dihydroxy-l,2,5,6-dibenzo-phenazine oli l-amino-2-methyl-5ch1orobenzen do Bl l 1-amino-2-phenoxy-5-ch1orob enzena do Darbtedbrowm l-amino-i-benzoylamino-5methoxy-2-chlorobenzene l-amiuo-4-benzoylamino-2 5-diethoxy-benzene l-amino-2-nitrobenzene i-amino-anthraquinone 4-ainino-4-methoxy-diphenylamine 4-amino-3,2-dimethyl-azo-benzene 4-ainino-2,fi-dimethoxy-4-nitro-azo-benzene 1-amino-2-n1ethyl-i-chlorobenzene Green-black.

i-amino-2-chloro-5-trifluormethylbenzene S-aminacarbazole 3-amino-benzophenone 1-amino-2,4,5trichlorobenzene 1-amino-2-(2,5-dichlorophenoxy)-5-ch1orobenzene rin Black-brown. do Red-brown. do Dark olive.

d Dark brown.

Brown. Black-brown.

17 l-amino-2-methyibenzene-5-(carbonyl-1-amino-2,S-dimeth- D oxybenzene) l8 Lamina-4b enzoyl-amino-2,5-dichiorobenzene -do D 19 Z-amino-l,6-dibromonaphthalene .J Do.

20 l-amino-3-methyl-2,4-dichlorobenzene do- Dark brown.

22 l-amino-2-chlorobenzene 4,8-d1hydroxy-Bz-2 -d br0m0-1,2,5,6-(11benz0- Black-oiive-brown.

phenazine.

23 1-amino-2,5'diohlorobenzene d Dark brown.

24 1-amino-2-methy1-5-chiorobenzene Dark olive.

25 l-amino-2-methyl-3-chlorobenzene- Do.

26 1-amino-2-methoxy-5-chlorobenzone" Do.

27 1-amin0-2-(4-chioropl1en0xy)-5-chior Do.

28 l-amino-2-methoxy-5-(diethyl-amino-sulionyl) -benzene Olive.

29 1-amino-2-phenyl-sul fonyl-benzene Red-brown.

30 i-amino-2-methyl-4-nitrobenzene Black-olive.

31 1-amino-2-methoxy-5-nitrobenzen Brown-olive.

Since an object of the present invention is to provide dyestufls of good fastness properties, which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of wherein X stands for hydrogen or bromine and R means a radical of the benzene series, yielding, when produced on the fiber, deep red-biown to black dyeings of good fastness properties.

3. The water-insoluble azo-dyestuff of the yielding, when produced on the fiber, a blackformula: brown dyeing.

(PC2115 5. The water-insoluble azo-dyestuff of the formula:

yielding, when produced on the: fiber, a blackishgreen dyeing. OOH: I

4. The water-insoluble azo-dyestuff of the yielding, when produced on the fiber, a dark formula: olive dyeing.

6. Fiber dyed with the azo-dyestuffs as claimed N=N 01 in claim 1.

7. Fiber dyed with the azo-dyestuffs as claimed OH; in claim 2.

r 8. Fiber dyed with the azo-dyestufi as claimed OH in claim 3.

9. Fiber dyed with the azo -dyestuff as claimed in claim 4. N 10. Fiber dyed with the azo-dyestufi as I I claimed in claim 5. N ARTHUR ZITSCI-IER. 

